Process for breaking emulsions of the oil-in-water class



Patented Mar. 11, 1952 PROCESS FOR BREAKING EMULSIONS OF THEOIL-IN-WATER CLASS Louis I. Monson, Puente, Calif., assignor toPetrolite Corporation, Ltd., Wilmington, Del., a corporation of DelawareNo Drawing. Application August 26, 1950,

Serial No. 181,699

1 This invention relates to a process for resolving or separatingemulsions of the oil-in-water class, by subjecting the emulsion to theaction of certain chemical reagents.

Emulsions of the oil-in-water class comprise organic oily materials,which, although immiscible with water or aqueous or non-oily media, aredistributed or dispersed as small drops throughout a continuous body ofnon-oily medium. The proportion of dispersed oily material is in manyand possibly most cases a minor one.

Oil-field emulsions containing small proportions ofcrude petroleum oilrelatively stably dispersed in water-or brine are representative oilin--water emulsions.

sions include: steam cylinder emulsions, in which traces of lubricatingoil are found dispersed in condensed steam from steam engines and steampumps; wax-hexane-water emulsions,

encountered in de-waxing operations in oil refining; butadienetar-in-water emulsions, in the manufacture of butadiene from heavynaphtha by cracking in gas generators, and occurring particularly in thewash =box waters of such systems; emulsions of flux oil in steamcondensate produced in the catalytic dehydrogenation of butylene toproduce butadiene; styrene-in-water emulsions, in synthetic rubberplants; synthetic latex-in-water emulsions, in plants producingcopolymer butadiene-styrene or GRS synthetic rubber; oil-in-wateremulsions occurring in the cooling' water systems of gasoline absorptionplants; pipe press emulsions from steam-actuated presses in clay pipemanufacture; emulsions of petroleum residues-in-diethylene glycol, inthe dehydration of natural gas.

In other industries and arts, emulsions of oily materials in water orother non-oily media are encountered, for example, in sewage disposaloperations, synthetic resin emulsion paint formulation, milk andmayonnaise processing, marine ballast -water disposal, and furniturepolish formulation. In cleaning the equipment used in processing suchproducts, diluted oil-in-water emulsions are inadvertently,incidentally, or accidentally produced. The disposal of aqueous wastesis, in general, hampered by the presence of 'o'il in-water emulsions.

Essential oils comprise non-saponifiable materials like terpenes,lactones, and alcohols. They also contain saponifiable esters ormixtures of saponifiable and non-saponifiable materials. Steamdistillation and other production procedures sometimes causeoil-in-water emulsions to be produced. from which the valuable essentialoils are difficultly recoverable.

In all such examples, a non-aqueous or oily cible. The term oil is usedherein to cover Other oil-in-water emu1 1 13 Claims. (01. 252-344)broadly the water-immiscible materials .present as dispersed particlesin such systems. The nonoily phase obviously includes diethylene glycol,aqueous solutions, and other non-oily media in addition to water itself.

The foregoing examples illustrate the fact that, within the broad genusof oil-in-water emulsions, there are at least three importantsub-genera. In these, the dispersed oily material is respectivelynon-saponifiable, saponifiable, and a mixture of non-saponifiable andsaponifiable materials. Among the most important emulsions ofnon-saponifiable material in water are petroleum oil-in-water emulsions.Saponifiable oil-in-water emulsions have dispersed phases comprising,for example, saponifiable oils and fats and fatty acids, and othersaponifiable oily or fatty esters and the organic components of suchesters to the extent such components are immiscible with aqueous media.Emulsions produced from certain blended lubricating compositionscontaining both mineral and fatty oil ingredients are examples of thethird sub-genus.

Oil-in-water emulsions contain widely different proportions of dispersedphase. Where the emulsion is a waste product resulting from the flushingwith water of manufacturing areas or equipment, the oil content may beonly a few parts per million. Resin emulsion paints, as produced,contain a major proportion of dispersed phase. Naturally-occurringoil-field emulsions of the oil-in-water class carry crude oil inproportions varying from a few parts per million to about 20%, or evenhigher in rare cases.

The present invention is concerned with the resolution of thoseemulsions of the oil-in-water class which contain a minor proportion ofdispersed phase, rangin from 20% down to a few parts per million.Emulsions containing more than about 20% of dispersed phase are commonlyof such stability as to be less responsive to the presently disclosedreagents, possibly because of the appreciable content of emulsifyingagent present in such systems, whether intentionally incorporated forthe purpose of stabilizing them, or not.

Although the present invention relates to emulsions containing as muchas 20% dispersed oily material, many if not most of them containappreciably less than this proportion of dispersed phase. In fact, mostof the emulsions encountered in the development of this invention havecontained about 1% or less of dispersed phase. It is to suchoil-in-water emulsions having dispersed phase volumes of the order of 1%or less to which the present process is particularly directed. This doesnot mean that any sharp line of demarcation exists and that, forexample, an emulsion containing 1.0% of dispersed phase will respond tothe process, whereas one containing 3 1.1% of the same dispersed phasewill remain unafiected; but that, in general, dispersed phaseproportions of the order of 1% or less appear most favorable forapplication of the present process.

In emulsions having high proportions of dispersed phase, appreciableamounts of some emulsifying agent are probably present, to account fortheir stability. In the case of more dilute emulsions, containing 1% orless of dispersed phase, there may be difiiculty in accounting for theirstability on the basis of the presence of an emulsifying agent in theconventional sense. For example, steam condensate frequently containsvery small proportions of refined petroleum lubricating oil in extremelystable dispersion; yet neither the steam condensate nor the refinedhydrocarbon oil would appear to contain anythingsuitable to stabilizethe emulsion. In such cases, emulsion stability must probably bepredicated on some basis other than the presence of an emulsifyingagent.

The present process, as stated above, appears to be effective inresolving emulsions containing up to about 20% of dispersed phase. It isparticularly effective on emulsions containing not more than.1% ofdispersed phase, which emulsions are the most important, in view oftheir common occurrence.

The present process is not believed to depend for its effectiveness onthe application of any simplelaws, because it'has a high level ofeffectiveness whenused to resolve emulsions of widely differentcomposition, e. g., crude or refined petroleum in Water or diethyleneglycol, as well as emulsions of oily materials like animal or vegetableoils or synthetic oily materials in water.

Some emulsions are by-products of manufacturing procedures in which thecomposition of the emulsion and its ingredients is known. Inmanyinstances, however, the emulsions to be resolved are eithernaturally-occurring or are accidentally or unintentionally produced; orin any event they do not result from a deliberate or'premeditatedemulsification procedure. In numerous instances, the emulsifying agentis unknown; and as a matter of fact an emulsifying agent, in theconventional sense, may be felt to be absent. It is obviously verydifficult or even impossible to recommend a resolution procedure for thetreatment'of such latter emulsions, on the basis of theoreticalknowledge. Many of the most important applications of thepresent processare concerned with the resolutionof emulsions which are eithernaturally-occurring or are accidentally, unintentionally,or unavoidablyproduced. Such emulsions are commonly of the most dilute type,containing about 1% or less of dispersed phase, although concentrationsup to 20% are herein included, as stated above.

The process which constitutes the present invention consists insubjecting an emulsion of the oil-in-water class to the action of areagent or demulsifier of the kind subsequently described, therebycausing the oil particles in the emulsion to coalesce sufiiciently torise to the surface of the non-oily layer (or settle to the bottom, ifthe oil density is greater), when the mixture is allowed to stand in thequiescent state after treatment with the reagent or demulsifier. I

Reference is made to my co-pending applications Serial Nos. 181,698 and181,700, both filed of even date, which relate to processes for the samepurpose as that of the present application and which employ reagentsrelated to the present reagents.

4 Applicability of the present process can be readily determined bydirect trial on any emulsion, without reference to theoreticalconsideror higher, are useful reactants here.

- face-active ations. This fact facilitates its application to naturallyoccurring emulsions, and to emulsions accidentally, unintentionally, orunavoidably produced; since no laboratory experimentation, to discoverthe nature of the emulsion components or of the emulsifying agent, isrequired.

The reagents employed as the demulsifiers in my process. includereaction products produced by the reaction of a poly-halogenated,nonionizedorganic compound and a surface-active poly-amino condensationpolymer, which latter material is, in turn, obtained by theheat-polymerization of a tertiary amino-alcohol of the formula: t

[HOR.(OR)m]n \N [R1]"' in which formula, OR is an alkylene oxide radicalhaving not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide radicals, propylene oxide radicals,butylene oxide radicals, 'glycide radicals, and meth'ylglycide radicals;R1 is a non-aromatic radical having 6 carbon atoms or less; m representa number varying from O to 3; n representsv the numeral 1, 2, or 3; andn represents the numeral 0, 1, or -2, with the proviso that n+n'=3; saidreaction resulting in the conversion, per molecule of poly-halogenatedreactant, of at least two halogen atoms from co-valent to electro-valentstate. The heat-polymerized aminoalcohol, in monomeric form, is atertiary amine containing at least one alkanol or hydroxyalkyl radical.

Such poly-amino reactants may be obtained, for example, by thepolymerization of triethanolamine, tripropenolamine, or the like, insuch a manner as to eliminate water and produce ether linkages. Suchpolymers may, in some cases, consist of dimers; but trimers, tetramers,or more'hig'hly polymerized forms, up to octamers They are characterizedby being surface-active, which means that their dilute solutions foam,reduce the surface tension of water, act as emulsifiers, etc. Theirexact composition cannot in all cases be depicted by theusualchemical-formulas, because they are poly-functional, they may be acyclicor alicyclic, and they are subject to wide variations. The primaryreaction is undoubtedly etherization. However, if some secondary amine,as, for example, diethanolamine or dipropanolamine, is present, watermay be eliminated by some reaction other than etherization, with theresult that 2 nitrogen atoms are united by an alkylene radical, asdistinguished from an alkyleneoxyalkylene radical.

Even though the exact structure of the surheat-polymerized alkanolaminesherein employed as reactants is not fully understood, their method ofmanufacture is well known, and they are used commercially for variouspurposes. The following description is typical of the conventionalpolymers.

The tertiary alkanolamines' having a single nitrogen atom, i. e.,monoamines, may be looked upon in simplest aspect as oxyalkylatedderivatives of ammonia. For example, although triethanolamine may bemanufactured invarious ways, it can be made by treating one mole ofammonia with 3 moles of ethylene oxide. An-

oxides containing a reactive ethylene oxide ring,

as, for example, propylene oxide, butylene oxide, glycide ormethylglycide, or mixtures of these various alkylene oxides. Suchproducts need not be derived directly from ammonia, but may be derivedfrom primary amines containing a radical having 6 carbon atoms or less,such as methylamine, ethylamine, propylamine, butylamine, amylamine, andhexylamine. For the present purpose, I specify that any such radicalpresent shall be nonaromatic. Aromatic radicals, if present, undesirablyreduce the basic character of the amine.

If a product like triethanolamine is treated with an excess of anoxyethylating agent like ethylene oxide, one introduces the oxyethyleneradical between a terminal hydrogen atom and the adjacent oxygen atom. 4Thus, ether-aminoalcohols obtained by reacting triethanolamine ortripropanolamine with one or two or even as many as nine moles ofethylene oxide are well known. The other similar ether-aminoalcohols arederived in the same manner and require no further description. Forpurposes of clarity, the tertiary amines herein included as rawmaterials for the polymerization step may be summarized by the followingformula:

wherein OR is an alkylene oxide radical having 4 carbon atoms or less,and preferably is the ethylene oxide radical. As indicated, OR may bethe propylene oxide radical, the butylene oxide radical, the glycideradical, or the methylglycide radical; R1 is a non-aromatic radicalhaving 6 carbon atoms or less; m represents a numeral varying from 0 to3; n represents the numeral 1, 2, or 3; and n represents the numeral 0,1, or 2, with the proviso that n+n'=3.

I prefer to use triethanolamine as my amino raw material. While thecommercial product contains moderate amounts of diand monoethanolamine,I have found it suitable.

It will be pointed out subsequently that the temperatures employed forpolymerization are commonly in the neighborhood of 250 C. This meansthat in most instances much of any monoor diethanolamine originallypresent may be volatilized and lost before having had an opportunity toreact. I have found no important difierence between polymers producedfrom chemically pure triethanolamine and those produced from commercialtriethanolamine having minor percentages of monoand diethanolaminepresent.

The poly-amino products obtained in the man ner herein described, whenmanufactured in iron vessels, are viscous, deep-amber-colored to darkbrown products. The degree of polymerization may be estimatedapproximately by the loss of water and the increase in viscosity.However, it is better to make an actual molecular weight determinationin the usual manner, for example, cryoscopically. The dimers as a classshow some surface-activity; if the product is heated further, withfurther loss of water and further increase in viscosity, the degree ofpolymerization and the level-of surface-activity are obviously higher.

Polymerization of the basic hydroxyamines is effected by heating atelevated temperatures, generally in the neighborhood of 250 0.,preferably inthe presence of catalysts like sodium hydroxide, potassiumhydroxide, sodium ethylate, sodium glycerate, or catalysts of the kindcommonly used in the manpfacture of superglycerinated fats and the like.The proportion of catalyst employed may vary from about 0.1%, in someinstances, to about 1% in others. If the aminoalcohol is low-boiling,precautions must be taken not to lose the material duringpolymerization. At the same time, water of reaction must be permitted tobe removed. At times, the process can be conducted most readily bypermitting a portion of the volatile constituents to distill, andsubsequently subjecting the vapors to condensation. The condenseddistillate contains water formed by the reaction. After removing suchwater from the distillate, e. g., by distilling with xylene, andseparating the xylene, the dried condensate may be returned to thereaction chamber for further processing. Sometimes, condensation is besteflected in the presence of a highboiling solvent, which is permitted todistill in such manner as to remove the water of reaction. In any event,the rate of reaction and the character of the polymerized product dependnot only on the original reactants, but also on the nature and amount ofcatalyst, the temperature and time of reaction, and the rateof waterremoval from the combining mass. Polymerization can be effected inabsence of catalysts, but the reaction usually takes appreciably longer,sometimes even at higher temperature.

The rate of reaction and the degree of polymerization are afiected bythe nature of the reaction vessel. In the examples cited below, itisintended that the reaction take place in a metal vessel such as iron. Inorder to obtain the same degree of polymerization in a glass vessel, thereaction time would usually have to be increased by nan-400%,

Surface-active, as herein employed and as generally used, refers tocompositions which are water-dispersible at least to the extent ofproducing a colloidal dispersion or sol. Thus, I do not contemplate theuse of products obtained by polymerization to the extent that they areno longer dispersible or miscible in water. In the case of some of mypoly-amino reactants, the degree of water-dispersibility andsurface-activity is low; but conversion into the final product byreaction with the poly-halogenatedreactant results in the formation of aproduct of desirably enhanced surface-activity.

Suitable amino raw materials, in addition to triethanolamine andtripropanolamine already mentioned, include ethyldiethanolamine,diethylethanolamine, propyldipropanolamine, dipropylpropanolamine,cyclohexyldiethanolamine, cyclohexyldipropanolamine, etc.

Other well known amines which may be employed are:

.N-cpHlo c3435 canon "OH ethanolamine and heat the mixture for 3 hours;

at 2'45- 250 C.,-with constant stirring. Condense any distillate andreserve for re-use'after'an'intermediate re-running dehydration step, asdescribed above. The reaction product is largely 'dimeric, asshown bymolecular weight determination.

POLY-AMINO REACTANT Example Use the procedure and reactants ofPoly-Amino'Reactant, Example 1, above, but continue the heating for 1.5hour longer. The reaction mass is largely the 'trirner, on a statisticalbasis.

POLY-AMINO REACTANT Example 3 Use the procedure and reactants ofPoly-Amino Reactant, Examples 1 and 2, above, but continue-heating untilincipient rubbering at reaction temperature occurs. The product, on theaverage has an average molecular weight equivalent to a mixture oftetrameric and pentameric polymers.

' POLY-AMINO REACTANT Example 4 Proceed as in Poly-Amino Reactant,Examples 1, 2, and 3, above, except substitute triisopropanolamine fortriethanolamine. The reaction proceeds more slowly; and extension of theheating periods to at least twice those specified in those examples isrequired.

As stated in Poly-Amino Reactant, Example 4, above, triisopropanolaminereacts more slowly than triethanolamine in this heat-polymerizationreaction. This may be due' to inaccessibility of the OH groups in thebranched-chain molecule. subjection of the amine to oxyalklation, e. g.,by reaction with ethylene'oxide prior to heat-polymerization, Willproduce an etherized alkanolamine which has longer alkanol radicals,more accessible in the heat-polymerization reaction.

'droxyl number. cl'ave and introduce ethylene oxide in'th'e ratioPOLY-AMINO REACTANT Example 5 React 1 'mole of triisopropanolamine with3 moles of ethylene oxide in an autoclave, using 1% of caustic soda as acatalyst and a temperature of about -165 C. afterthe pressure in thevessel returns to normal, (it will rise immediate- 1y after addition ofthe ethylene oxide to as much as 50 p. s. i. g.; but will fall again asthe oxide reacts), raise the temperature to about 250 C. and continueheating for 5, 8 and 10 hours, re-

spectively, to attain 3 different levels of polymerization. The vesselis left open during the 250 C. heating. This is also true for Examples 6and 7 below.)

lOL-Y-AMINO REACTANT Example 6 Prepare a polyethanolarnine of theformula:

2 4O 2HlOH N-o2moo2rn0i1 2HlOC2H4OH by reacting 1 mole oftriethanolamine and 3 moles of ethylene oxide in an autoclave, as justdescribed in Example 5, above. Then heat this product at about 250C.'for 3 hours, 4.5 hours,

and to incipient rubbering, as described in Poly- Amino Reactant,Examples 1, 2 and 3, to attain three different levels ofheat-polymerization.

POLY-AMINO REACTANT Example 7 RepeatPoly-Amino Reactant, Example 6,ex-

cept use 9 moles of ethylene oxide and 1 mole of triethanolamine toproduce a polyethanolamine of the formula:

V C2H4O(C'2H4O)3H v Heat'this product at about 250 C. for periods of 3hours, 4.5 hours, and to incipient rubbering, respectively, as inPoly-Amino Reactant, Examples 1, 2, and 3, to attain three differentlevels of heat-polymerization.

' POLY-AMINO REACTANT Example 8 Prepare a heat-polymerizedtriethanolainine by'following the procedure of Poly-Amino Reactant,Examples 1, 2, or 3. Determine'its hy- Place the product in an' autoof 1mole for each OH group present,'using a temperature ofabout C. and 1% ofcaustic soda as a catalyst, as in Example 5, above.

POLY-AMINO REACTANT "Erample 9 "Repeat. Poly-Amino Reactant, Example 3,'but introduce, respectively, 2 and 3 moles of ethylene oxide for eachOH group.

If desired, mixed alkylene oxides may bej emplayed; to produce theseoxyalkylated amino marine per molecule.

amine at about 250 C., with or without catalyst, to be a widely usefulpoly-amino reactant for producing my finished reagents. I have foundthat the dimer produced by heat-polymerizing triethanolamine issuitable, especially where the polyhalogenated reactant is of relativelyhigher molecular weight. I have found that when one approachespentamersin the heat-polymerization of commercial triethanolamine, one hasachieved a relatively high viscosity, approaching rubbering, even atpolymerization temperature. My especially preferred poly-amino reactantsare therefore prepared by heat-polymerizing commercial triethanolamineuntil the material comprises, on the average, dimers through pentamers.Where one of the radicals linked to the nitrogen atom is, for example,an alkyl radical of or 6 carbon atoms, a substantial plasticizing effectmay be observed, which will permit con- .tinuing heat-polymerizationsomewhat further before rubbering occurs. In general, I have found thatwhen the molecular weight of the amino heat-polymer exceeds about 1,000,it often produces an inferior reaction product; and that when it exceeds2,000, the reaction products produced from it and the polyhalogenatedreactants are not vparticularly effective for the present purpose. I,therefore, disclaim the use of poly-amino reactants of molecular weightgreater than this figure.

My reagents are produced from heat-polymerized tertiary alkanolamines ofthe kind just described in detail, by reacting them with a wide varietyof polyhalogenated non-ionized organic halogen atoms in the molecule arelikewise useful reactants for the present purpose. For exam- .ple,paraflin may be chlorinated to introduce large proportions of thatelement. Commercially these are offered by Hooker ElectrochemicalCorporation, as, for-example, CP 40,? CP 50, and

CP 70, the designations bein understood to mean Chlorinated Paraffin,approximately 40% chlorine 'conten etc. The actual chlorine contents ofsuch products are quite close to the percentages suggested by suchdesignations. The

product CP 40, for example, contains about 42% chlorine, equivalent toabout 7.5 atoms of chlo- CP 50 contains about 9 atoms of chlorine permolecule; and CP '70 contains about 21 atoms of chlorine per molecule.All these products are useful reactants here.

The poly-halogenated reactant need not be a halogenated hydrocarbon,however. Very good results have been obtained'from products obtainedfrom dichloromethyl etheiydichloroethyl ether, dichloroisopropyl ether,a mixture of dichloroethyl ether and dichloroisopropyl ether (availableunder the trade name Betachlor from Wyandotte Chemical Corporation)dibromoethyl ether, glycerol dichlorohydrih, triglycol dichloride; etc.

A convenient means for preparing other poly POLY-HALOGENATED REACTANTExample 1 Glycerol (1 mole) is mixed with 1% of stannic chloride andreacted with 3 moles of epichlorohydrin. The reaction evolves heat andshould be conducted cautiously at minimum temperature. A temperature ofless than C. suffices. The'product is a trichloro reactant suitable forthe present purpose.

POLY-HALOGENATED REACTANT Example 2 Glycerol (1 mole) is reacted with 3moles of ethylene oxide in an autoclave, using 1% caustic soda as acatalyst and a temperature of about C. The product is neutralized, 1%stannic chloride is added, and 3 moles of epichlorohydrin areintroduced, at about 90 C., as in Poly-Halogenated Recatant, Example 1,above.

POLY-HALOGENATED REACTANT Example 3 Substituted erythritrol for glycerolin Poly- Halogenated Reactant, Examples 1 and 2, just above.

Other examples could be recited, showing the use of diglycerol, ethyleneglycol, polyethylene glycols, polypropylene glycols, etc., as startingmaterials which can be converted through the medium of epichlorohydrininto poly-halogenated reactants useful in producing my finishedreagents. The foregoing examples sufiice to illustrate but obviously donot exhaust the field of useful poly-halogenated reactants. v

I specifically include poly-iodo and poly-fiuoro compounds among myclass of poly-halogenated reactants.

I exclude from my class of useful poly-halogenated reactants ionizablepoly-halogenated organic compounds, such as dichloroacetic acid andtrichloroacetic acid.

I likewise exclude poly-halogenated aromatic compounds wherein thehalogen atoms are attached directly to the aromatic ring. Use of suchreactants would result in the presence, in the finished product, of anaromatic ring directly linked to nitrogen; this I have foundundesirable. Among such aromatic poly-halogenated materials specificallyexcluded is dichlorobenzene. Dichlorobenzoic acid is excluded, both forthe reason that it has halogen attached directly to the ring and alsobecause it is ionizable.

To prepare my finished reagents, one need only react one or more membersof my class of polyamino reactants with one or more members of my classof poly-halogenated reagents at a suitable temperature, and in suitableproportions, for a suitable time, as explained below. The temperaturerequired in any case should be determined cautiously, as the reactioninvolved is usually exothermic, and the mass may reacttoo vigorously,with production of a'rubbery or even somewhat pyrolized material oflittle utility. For example, when dichloroethyl ether andheatpolymerized triethanolamine are reacted, a temperature of about 110C.'is required; but if the temperatureexceeds about 125 ,C.,-it isusually uncontrollable, and the batch may be spoiled for the presentpurpose, quickly going to a rubbery stage.

The simplest way to follow the course of the reaction between mypoly-amino reactants and my poly-halogenated reactants is based on thefact that, as the reaction proceeds, halogen atoms which were originallypresent in un-ionized or co-valent form are converted to ionic orelectrovalent halogen atoms. Determination of ionic halogen is, ofcourse, asimple analytical procedure, requiring only titration withsilver nitrate.-

If one starts with a di-arnino reactant and a (ii-halogenated reactant,for example, and determines by analysis of samples taken during thecourse of the reaction that one-half or less of the halogen present hasbeen converted from the co-valent or un-ionized state to theelectro-valent or ionized state, one of the two halogens originallypresent has been reacted, but the second remains unreacted. As heatingis continued, more and more of the halogen content is converted to theionized state.

It is usually possible to convert all the halogen present, unless thereis an excess of the halogenated reactant. For example, if a di-aminoreactant and a' (ii-halogenated reactant are used in molal proportionsor in proportions where there is a deficiency of the halogenatedmaterial, the proportion of ionic halogen increases as the reaction iscontinued. Substantially complete conversion of halogen from theun-ionized to ionized state is accomplished. Where a diami'no reactantand a tri-halogenated reactant ar us d, obviously the last one of thethree halogen atoms will not be converted; and substantiallycompletereaction is indicated by conversion of two-thirds of the originalhalogen. If, on the other hand, a tri-amino reactant and adihalog'enated reactant are used, the conversion of halogen is somewhatmore readily accomplished.

In general, in preparing my reagents, I prefer to have present a molalexcess of the amino reactant, and to control by analysis the degree ofconversion of halogen atoms from the un-ionized or co-valent state tothe ionized or electro-valent state.

While I usually employ a single poly-amino reactant and a singlepoly-halogenated reactant to produce my reagents, it is perfectlypossible, as stated above, to employ a mixture of amino reactants and amixture of halogenated reactants to produce them. I

In many applications of reagents of this general class to the resolutionof oil-in-water emulsions, I have found it important that not more thanone halogen atom per molecule of poly-halogenated reactant be convertedin this reaction. One

possible explanation of this fact is that under such circumstances therecan be no bridging or casions when it is found that increasing themoimpioves the results obtained when it is used as an oil-in-waterdemulsifier. For example, if both the poly-amino reactant and thepoly-halogenated reactahtare of relatively low 'molecular weight, it maybe desirable to secure bridging or cross-linking to build a larger andbranched molecule of increased effectiveness. Inorder to accomplish suchbridging or cross-linking, at least 2 halogen atoms of thepoly-halogenated reactant must be involved in the reaction by which myreagent is prepared.

I have limited my present invention to the use of reagents includingthose reaction products of my poly-amino reactants and mypoly-halogen'ated reactants in which at least two halogen atoms perpoly-halogenated reactant molecule have been converted from theco-valentor unionized state to the electro-valent or ionized state. Includedamong typical examples of my present products are:

REACTION PRODUCT EztampZe 1 withdrawn after this time was titrated withsilver nitrate and showed 71.7% of the chlorine had been converted tothe ionic state. Since 33.3% would represent conversion of 1 chlorineper molecule of chloroform, more than two atoms per molecule had beenconverted, on a statistical basis, when 71.7% conversion wasaccomplished, as noted. The product was an effective oil-inwaterdemulsifier.

REACTION PRODUCT Example 2 The poly-amino reactant of Reaction Product,Example 1, above, (280 pounds) was mixed with 57.5 pounds of carbontetrachloride. The mixture was heated 2.5 hours, the temperature goingas high as 145 C. during this period. Titration of a sample with silvernitrate showed 57.2% of the chlorine had been converted to the ionicstate. This is slightly over 2 chlorine atoms per molecule of carbontetrachloride, on the average. Heating was continued 2.3 hours, and asecond sample was titrated with silver nitrate as before. It showed70.5% conversion of chlorine to the ionic state. Heating was continuedfor 2.5 hours longer; By the end. of the time, 80.1% of the chlorine hadbeen converted to the ionic state. All three products were effectiveoil-in-water demulsifiers.

REACTION PRODUCT Example 3 A heat-polymerized commercial triethanolamine(302 pounds), prepared as in Reaction Product, Example 1, above, wasmixed with dichloroethyl ether (57.4 pounds); and the mixture was heated4 hours at a temperature of from to 132 C. At the end of this time, asample titrated with silver nitrate showed conversion of 82.0% of thechlorine had been accomplished. Further heating for 3.2 hours attemperatures between and 163 C. produced a sample,

Example 4 Heat-polymerized commercial triethanolamine (280 pounds),prepared as in Reaction Product, Example 1, and 65.6 pounds oftriglycoldichloride were heated for 5.5 hours, the temperature beingheld at about 165 C. most of this time. Titration I with silver nitrateshowed 76.3% of the chlorine had been converted to the ionic state. Thismeans that, in about half of the halogenated molecules, both chlorineatoms had been converted. The product was an effective oil-in-waterdemulsifier.

REACTION PRODUCT Example 5 Mix 280 pounds of heat-polymerized commercialtriethanolamine, prepared as in Reaction Product, Example 1, above, and63.6 pounds of dichloroisopropyl ether. Heat for 12.5 hours, the

silver nitrate. The product was an effective oilin-water demulsifier.

REACTION PRODUCT Example 6 Mix 280 pounds of heat-polymerized commercialtriethanolamine, prepared as in Reaction Product, Example 1, above, and53 pounds of the chlorinated paraffin sold by Hooker Electrochem- 14about 160 C. for 1 hour; at 200 C. for another 18 hours. The granularcrystalline precipitate which formed in the early stages of the reactionslowly decreased in amount as heating continued. The degree ofconversion of chlorine finally achieved was approximately 75%, to theionized state. (This means that both chlorine atoms of half thedichloroethyl ether molecules had been converted to the ionic state.)The product was an effective oil-in-water demulsifier.

The present reagents are useful because they are able to recover the oilfrom oil-in-water class emulsions more advantageously and at'lower costthan is possible using other reagents or other processes. In someinstances, they have been found to resolve emulsions which were noteconomically or effectively resolvable by any other known means.

My reagents may be employed in undiluted form or they may be useddiluted with any suitable solvent. Water is commonly found to be ahighly satisfactory solvent, because of its ready ical Company, NiagaraFalls, N. Y., under the trade name CP 40. Heat at a temperature notexceeding 200 C. until titration with silver nitrate shows one-third ofthe chlorine has been converted to the ionic state. (Since the productcontains approximately 42.5% chlorine, equivalent to about 7.5 chlorineatoms per molecule, on the average, this degree of conversion isequivalent to the conversion of about 2.5 of the 7.5

chlorine atoms present per molecule.) The product is an effectiveoil-in-water demulsifier.

REACTION PRODUCT Example 7 ture of 250 C. until determination of thehydroxyl number by the Verley-Btllsing method, .1

shows a decline of hydroxyl content to one-half the original value.React the poly-amino mate'- rial so prepared, 248 pounds, and thepoly-chlorinated glycerol material produced in Poly-HalogenatedReactant, Example 1, pounds, at

C. until the degree of conversion of the chlorine is found by silvernitrate titration to be two:

thirds.

(The original chlorine content of the mixture can be determined, forexample, by the I Parr bomb method for total chlorine.) product is aneffective oil-in-water demulsifier.

REACTION PRODUCT Example 8 Commercial triethanolamine (280 pounds) andThe:

dichloroethyl ether (53 pounds) were heated inan iron vessel withstirring, the temperature :being held at about l20-125 C. for 6 hours;at

- separates.

availability and negligible cost; but in some cases, non-aqueoussolvents such as aromatic petroleum solvent may be found preferable. Theproducts themselves may exhibit solubilities ranging from rather modestwater-dispersibility to full and complete dispersibility in thatsolvent. Because of the small proportions in which my reagents arecustomarily employed in practising my process, apparent solubility inbulk has little significance. In the extremely low concentrations of usethey undoubtedly exhibit appreciable water-solubility orwater-dispersibility as well as oil-solubility or oil-dispersibility.

My reagents may be employed alone, or they may in some instances beemployed to advantage admixed with other and compatible oil-in-waterdemulsifiers. Specifically, I have found they 'may be advantageouslyadmixed with the reagents disclosed in U. S. Patents Nos. 2,159,312 and2,159,313, both dated May 23, 1939,v to Blair and to Blair and Rogers,respectively. One 'useful mixture of this sort incorporates the productof Reaction Product, Example 9, above, glue, and calcium chloride.Likewise, they may be used in admixture with the reagents disclosed andclaimed in my above-mentioned co-pending application, Serial No.181,698, filed of even date herewith.

My process is commonly practised simply by introducin small proportionsof my reagent into an oil-in-water class emulsion, agitating to securedistribution of the reagent and incipient coalescence, and letting standuntil the oil phase The proportion of reagent required will vary withthe character of the emulsion to be resolved. Ordinarily, proportionsof. reagent required are from fl to ipgmqng the volume of emulsiontreated; but more is sometimes required. I have found that the factors,reagent feed rate, agitation, and settling time are somewhatinterrelated. For example, I have found that if sufiicie'nt agitation ofproper character is employed,.the settling time is shortened materially.On the other hand, if satisfactory agitation is not available, butextended settling time is, the process is equally productive ofsatisfactory re sults.

Agitation may be achieved by any available means. In many cases, it issufiicient to introduce the reagent into the emulsion and use theagitation produced as the latter flows through a conduit .or pipe. Insome cases, agitation and mixing are achieved by stirrin together orshaking together the emulsion and reagent. In some instances, distinctlyimproved results are obtained by the use of air or other gaseous medium.Where the volume of gas employed is relatively small and the conditionsof its introduction relatively mild, it behaves as a means of securingordinary agitation. Where aeration is effected by introducing a gasdirectly under pressure or from porous plates or by means of aerationcells, the effect is often importantly improved, until it constitutes adiiference in kind rather than degree. A sub-aeration type flotationcell, of the kind commonly employed in ore beneficiation operations, isan extremely useful adjunct in the application of my reagents to manyemulsions. It frequently accelerates the separation of the emulsion,reduces reagent requirements, or produces an improved effluent.Sometimes all three improvements are observable.

Heat is ordinarily of little importance in resolving oil-in-water classemulsions with .my reagents. Still there are some instances where heatis a useful adjunct. This is especially true where the viscosity of thecontinuous phase of the emulsion is appreciably higher than that ofWater.

In some instances, importantly improved results are obtained byadjusting the pH of the emulsion to be treated, to an experimentallydetermined optimum value.

The reagent feed rate also has an optimum range, which is sufiicientlywide, however, to meet the tolerances required for the variancesencountered daily in commercial operations. A large excess of reagentcan produce distinctly unfavorable results.

The manner of practising the present invention is clear from theforegoing description. However, for completeness the following specificexample is included. The oil-in-water class emulsion in question wasbeing produced from an oil well. It contained about 1,500parts-per-million of crude oil, on the average, and was stable for daysin absence of any attempt to resolve it. My

process was practised at this location by flowing the well fluids,consisting of free crude oil, oil-inwater emulsion, and natural gas,through a gas separator, then to a steel tank of 5,000-barrel capacity.In this tank, the oil-in-rwater emulsion fell to the bottom and was soseparated from the free oil. The oil-in-water emulsion was withdrawnfrom the bottom of this tank, and the reagent of Reaction Product,Example 3, above, was introduced into the stream at this point. Theproportion employed was about 1/9(),Q()0 the volume of emulsion, on theaverage. The chemicalized emulsion flowed to a second tank, mixing beingachieved in the pipe. In the second tank it was allowed to standquiescent. Clear water was withdrawn from the bottom of this tank,separated oil from the top.

My reagents have likewise been successfully applied to otheroil-in-water class emulsions, of which representative examples have beenreferred to above. Their use is, therefore,.not limited to crudepetroleum-in-water emulsions.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is:

l.A process for breaking emulsions composed of an oil-dispersed in anon-oily continuous phase, in which the dispersed phase is not greaterthan 20%, characterized by subjecting the emulsion to the action of areagent including a reaction product produced by the'reaction between apoly-halogenated non-ionized organic compound in which the halogen atomsare not attached directly to an aromatic ring and a surface-activecondensation polymer of mean molecular weight not in excess of 2,000,which latter is in turn obtained by the heat-polymerization of atertiary aminoalcohol of the formula:

HO R. on m n in which formula, OR is an alkylene oxide radical havingnot more than 4 carbon atoms and selected from the class consisting ofethylene oxide radicals, propylene oxide radicals, butylene oxideradicals, glycide radicals, -and methylglycide radicals; R1 is anon-aromatic hydrocarbon radical having 6 carbon atoms or less;-mrepresents a number varying from 0 to 3; n represents the numeral 1, 2,or 3; and n represents the numeral 0, 1, or 2, with the proviso thatn+n':3; said reaction resulting in the conversion, per molecule ofpoly-halogenated reactant, of at least two. halogen atoms from theco-valent to the electr-o-valent state.

2. A process for breaking oil-in-water emulsions, in which the dispersedphase is not greater than 20%, characterized by subjecting the emulsionto the action of a reagent including a reaction product produced by thereaction between a poly-halogenated non-ionized organic compound inwhich the halogen atoms are not attached directly to an aromatic ringand a surface-active condensation polymer of mean molecular weight notin excess of 2,000, which latter is in turn obtainedby theheat-polymerization of a tertiary aminoalcohol of the formula:

in which formula, OR is an alkylene oxide radical having not more than 4carbon atoms and selected from the class consisting of ethylene oxideradicals, propylene oxide radicals, butylene oxide radicals, glycideradicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbonradical having 6 carbon atoms or less; m represents a number varyingfrom 0 to 3; n represents the numeral '1, 2, or 3; and n represents thenumeral 0, 1, or 2, with the proviso that n+n' 3; said reactionresulting in the conversion, per molecule of poly-halogenated reactant,of at least two halogen atoms from the co-valent to the electro-valentstate.

3. A process for breaking oil-in-water emulsions, in which the dispersedphase is not greater than 1%, characterized by subjecting the emulsionto the action of a reagent including a reaction product produced by thereaction between a poly-halogenated non-ionized organic compound inwhich the halogen atoms. are not attached directly to an aromatic ringand a surface-active condensation polymer of mean molecularweight not inexcess of 2,000, which latter is in turn obtained by theheat-polymerization of a tertiary aminoalcohol of the formula:

in which formula, OR is an alkylene oxide radical having not more than 4carbon atoms and selected from the class consisting of ethylene oxideradicals, propylene oxide radicals, butylene oxide radicals, glycideradicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbonradical having 6 carbon atoms or less; m represents a number varyingfrom to 3; n represents the numeral 1, 2, or 3; and n represents thenumeral 0, 1, or 2, with the proviso that n+n':3; said reactionresulting in the conversion, per molecule of poly-halogenated reactant,of at least two halogen atoms from the co-valent to the electro-valentstate.

4. A process for breaking petroleum oil-inwater emulsions, in which thedispersed phase is not greater than 1%, characterized by subjecting theemulsion to the action of a reagent including a reaction productproduced by the reaction between a poly-halogenated non-ionized organiccompound in which the halogen atoms are not attached directly to anaromatic ring and a surface-active condensation polymer of meanmolecular weight not in excess of 2,000, which latter is in turnobtained by the heatpolymerization of a tertiary aminoalcohol of theformula:

in which formula, OR is an alkylene oxide radical having not more than 4carbon atoms and selected from the class consisting of ethylene oxideradicals, propylene oxide radicals, butylene oxide radicals, glycideradicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbonradical having 6 carbon atoms or less; m represents a number varyingfrom 0 to 3; n represents the numeral 1, 2, or 3; and n represents thenumeral 0, 1, or 2, with the proviso that n+n=3; said reaction resultingin the conversion, per molecule of poly-halogenated reactant, of atleast two halogen atoms from the co-valent to the electro-valent state.

5. The process of claim 4, wherein n is 0.

6. The process of claim 4, wherein both 11. and m are 0.

7. The process of claim 4, wherein both n and m are 0, and OR is theethylene oxide radical.

8. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized triethanolamine.

9. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized commercial triethanolamine of meanmolecular weight not in excess of 2,000.

10. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized commercial triethanolamine of meanmolecular weight not in excess of 2,000 and the poly-halogenatednon-ionized organic compound is chloroform.

11. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized commercial triethanolamine of meanmolecular weight not in excess of 2,000 and the poly-halogenatednon-ionized organic compound is dichloroethyl ether.

12. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized commercial triethanolamine of meanmolecular weight not in excess of 2,000 and the poly-halogenatednon-ionized organic compound is carbon tetrachloride.

13. The process of claim 4, wherein the heatpolymerized aminoalcoholreactant is a heatpolymerized commercial triethanolamine of meanmolecular weight not in excess of 2,000 and the poly-halogenatednon-ionized organic compound is chlorinated parafiin.

LOUIS T. MONSON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,159,312 Blair May 23, 19392,159,313 Blair et al May 23, 1939 2,407,895 Monson et al Sept. 17, 19462,470,829 Monson May 24, 1949

1. A PROCESS FOR BREAKING EMULSIONS COMPOSED OF AN OIL-DISPERSED IN ANON-OILY CONTINUOUS PHASE, IN WHICH THE DISPERSED PHASE IS NOT GREATERTHAN 20%, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF AREAGENT INCLUDING A REACTION PRODUCT PRODUCED BY THE REACTION BETWEEN APOLY-HALOGENATED NON-IONIZED ORGANIC COMPOUND IN WHICH THE HALOGEN ATOMSARE NOT ATTACHED DIRECTLY TO AN AROMATIC RING AND A SURFACE-ACTIVECONDENSATION POLYMER OF MEAN MOLECULAR WEIGHT NOT IN EXCESS OF 2,000,WHICH LATTER IS IN TURN OBTAINED BY THE HEAT-POLYMERIZATION OF ATERTIARY AMINOALCOHOL OF THE FORMULA: